Solid catalyst component for olefin polymerization

ABSTRACT

A solid catalyst component for olefin polymerization, comprising titanium atoms, magnesium atoms, halogen atoms and hydrocarbyloxy groups, wherein the following filtrate contains titanium atoms in a concentration of 0.08 mg-Ti/ml-filtrate or lower, measured according to a method comprising the steps of (1) preparing a suspension of the solid catalyst component for olefin polymerization in heptane having a concentration of 0.1 g-solid catalyst component/ml-suspension, (2) heating the suspension at 70° C. for 30 minutes under stirring, (3) filtering the suspension, thereby obtaining a filtrate, and (4) measuring a concentration of titanium atoms contained in the filtrate; and a production process of the solid catalyst component.

FIELD OF THE INVENTION

The present invention relates to a process for producing a solidcatalyst component for olefin polymerization, a process for producing anolefin polymerization catalyst, and a process for producing an olefinpolymer.

BACKGROUND OF THE INVENTION

JP 10-212319A (corresponding to U.S. Pat. No. 6,187,883B) discloses ahighly stereoregular olefin polymer produced by polymerizing an olefinin the presence of a polymerization catalyst, the catalyst being formedaccording to a process comprising the steps of (1) reducing a titaniumcompound with an organomagnesium compound in the presence of acombination of an organosilicon compound with an ester compound, therebyproducing a solid product, (2) contacting the solid product with ahalogenation compound, an internal electron donor and an organic acidhalide, thereby producing a solid catalyst component containingtrivalent titanium atoms, and (3) contacting the solid catalystcomponent containing trivalent titanium atoms, an organoaluminumcompound and an external electron donor.

SUMMARY OF THE INVENTION

However, the above highly stereoregular olefin polymer is not sufficientin stiffness of its injection-molded article, namely, is not sufficientin its stereoregularity, whereas injection-molded articles havingsuperior stiffness are particularly required.

In view of the above circumstances, the present invention has an objectto provide:

(i) a solid catalyst component for olefin polymerization capable ofproducing a highly stereoregular olefin polymer, which can be moldedinto an injection-molded article having superior stiffness;

(ii) a process for producing the above solid catalyst component (i);

(iii) a process for producing an olefin polymerization catalyst usingthe above solid catalyst component (i); and

(iv) a process for producing an olefin polymer using an olefinpolymerization catalyst produced according to the above process (iii).

The present invention is a solid catalyst component for olefinpolymerization, comprising titanium atoms, magnesium atoms, halogenatoms and hydrocarbyloxy groups, wherein the following filtrate containstitanium atoms in a concentration of 0.08 mg-Ti/ml-filtrate or lower,measured according to a method comprising the steps of:

(1) preparing a suspension of the solid catalyst component for olefinpolymerization in heptane having a concentration of 0.1 g-solid catalystcomponent/ml-suspension;

(2) heating the suspension at 70° C. for 30 minutes under stirring;

(3) filtering the suspension, thereby obtaining a filtrate; and

(4) measuring a concentration of titanium atoms contained in thefiltrate.

Also, the present invention is a process for producing the above solidcatalyst component for olefin polymerization, comprising the followingsteps (1) and (4) in this order, or comprising the following step (1),one or more repetitions of a combination of the following steps (2) and(3) in this order, and the following step (4), in this order:

(1) contacting a solid material containing magnesium atoms andhydrocarbyloxy groups, a halogenation compound and an internal electrondonor and/or organic acid halide with one another, thereby obtaining asolid component;

(2) washing the solid component with a hydrocarbon solvent;

(3) contacting the washed solid component, a halogenation compound, andan internal electron donor and/or organic acid halide with one another;and

(4) washing the solid component with a hydrocarbon solvent at 70° C. orhigher four or more times.

Further, the present invention is a process for producing an olefinpolymerization catalyst, comprising the step of contacting a solidcatalyst component for olefin polymerization produced according to theabove production process, an organoaluminum compound and an externalelectron donor with one another.

Furthermore, the present invention is a process for producing an olefinpolymer, comprising the step of contacting an olefin with an olefinpolymerization catalyst produced according to the above productionprocess.

DETAILED DESCRIPTION OF THE INVENTION

As explained above, the process of the present invention for producing asolid catalyst component for olefin polymerization has two embodiments.The first embodiment comprises the above steps (1) and (4), and thosesteps are carried out in this order. The second embodiment comprises theabove step (1), one or more repetitions of a combination of the abovesteps (2) and (3), and the above step (4), and those steps are carriedout in this order. In case that the second embodiment has tworepetitions of a combination of the above steps (2) and (3), all thesteps are carried out in the following order:

-   -   step (1)→step (2)→step (3)→step (2)→step (3)→step (4).        It should be noted that both embodiments have the step (4) after        the step (1) in case of the first embodiment, or after the final        step (3) in case of the second embodiment.

Regarding the Step (1):

The solid component obtained in the step (1) may be known in the art,which is disclosed in prior arts such as JP 10-212319A corresponding toU.S. Pat. No. 6,187,883B and JP 7-216017A corresponding to U.S. Pat. No.5,608,018A.

Examples of the solid material used in the step (1) are the followingsolid materials (i) to (iii), and the solid material (iii) is preferableamong them:

(i) dihydrocarbyloxymagnesiums represented by the formula, Mg(OR¹)(OR²),wherein R¹ and R² is independently of each other a hydrocarbyl grouphaving 1 to 20 carbon atoms;

(ii) hydrocarbyloxymagnesium halides represented by the formula, Mg(OR³)X¹, wherein R³ is a hydrocarbyl group having 1 to 20 carbon atoms, andX¹ is a halogen atom; and

(iii) solid materials containing trivalent titanium atoms, magnesiumatoms and hydrocarbyloxy groups.

Examples of the dihydrocarbyloxymagnesiums represented (i) by the aboveformula, Mg(OR¹)(OR²), are dimethoxymagnesium, diethoxymagnesium,dipropoxymagnesium, dibutoxymagnesium, dipentoxymagnesium,dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium,dicyclohexyloxymagnesium, methoxyethoxymagnesium,methoxypropoxymagnesium, methoxybutoxymagnesium, ethoxypropoxymagnesium,and ethoxybutoxymagnesium. Among them, preferred is dimethoxymagnesium,diethoxymagnesium or dipropoxymagnesium, and more preferred isdiethoxymagnesium.

A process for producing dihydrocarbyloxymagnesiums (i) represented bythe above formula, Mg(OR¹)(OR²), is not limited. Preferable examplesthereof are (1) a process comprising the step of reacting a magnesiummetal, an alcohol and a small amount of a halogen-containing compoundand/or halogen, with one another, and (2) a process comprising the stepof reacting a dialkylmagnesium compound with an alkoxysilicon compound.

Examples of the hydrocarbyloxymagnesium halides (ii) represented by theabove formula, Mg(OR³)X¹, are methoxymagnesium chloride, ethoxymagnesiumchloride, propoxymagnesium chloride, butoxymagnesium chloride,pentoxymagnesium chloride, hexyloxymagnesium chloride, octoxymagnesiumchloride, phenoxymagnesium chloride, and cyclohexyloxymagnesiumchloride, and compounds obtained by replacing the chlorine atomcontained in the above-exemplified compounds with a fluorine atom, abromine atom or a iodine atom. Among them, preferred is methoxymagnesiumchloride, ethoxymagnesium chloride or propoxymagnesium chloride, andmore preferred is ethoxymagnesium chloride.

A process for producing hydrocarbyloxymagnesium halides (ii) representedby the above formula, Mg(OR³)X¹, is not limited. Preferable examples ofthe process are (1) a process comprising the step of reacting a Grignardcompound with an alkoxysilicon compound, and (2) a process comprisingthe step of reacting a Grignard compound with alcohol.

Examples of the hydrocarbyloxy group contained in the above solidmaterials (iii) are hydrocarbyloxy groups having 1 to 20 carbon atoms.Among them, preferred is a methoxy group, an ethoxy group, a propoxygroup, a butoxy group, a pentoxy group, or a hexoxy group.

The solid material used in the step (1) is preferably the above solidmaterial (iii), which contains the trivalent titanium atoms in an amountof preferably 50% or more, and more preferably 90% or more, providedthat the total amount of titanium atoms contained in the solid material(iii) is 100%, and contains the hydrocarbyloxy groups in an amount ofpreferably 20% by weight or more, and more preferably 25% by weight ormore, provided that the amount of the solid material (iii) is 100% byweight.

A process for producing the solid material (iii) comprises, for example,the step of reducing a titanium compound represented by the followingformula [I] with an organomagnesium compound in the presence of anorganosilicon compound containing a Si—O bond, or in the presence of acombination of the organosilicon compound with an ester compound in viewof improving an activity of a polymerization catalyst:

wherein R⁴ is a hydrocarbyl group having 1 to 20 carbon atoms; X² isindependently of one another a halogen atom or a hydrocarbyloxy grouphaving 1 to 20 carbon atoms; and a is a number of 1 to 20, andpreferably a number satisfying 1≦a≦5.

Examples of R⁴ in the above formula [I] are an alkyl group such as amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, an amyl group, an isoamyl group, a hexylgroup, a heptyl group, an octyl group, a decyl group and a dodecylgroup; an aryl group such as a phenyl group, a cresyl group, a xylylgroup and a naphthyl group; a cycloalkyl group such as a cyclohexylgroup and a cyclopentyl group; an allyl group such as a propenyl group;and an aralkyl group such as a benzyl group. Among them, preferred is analkyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 18carbon atoms, and particularly preferred is a linear alkyl group having2 to 18 carbon atoms.

Examples of the halogen atom of X² in the above formula [I] are achlorine atom, a bromine atom and an iodine atom. Among them,particularly preferred is a chlorine atom.

Examples of the hydrocarbyloxy group having 1 to 20 carbon atoms of X²in the above formula [I] are those derived from the above-exemplifiedhydrocarbyl groups as R⁴, such as a methoxy group derived from a methylgroup, an ethoxy group derived from an ethyl group, etc. Among them,particularly preferred is an alkoxy group derived from theabove-exemplified linear alkyl group having 2 to 18 carbon atoms as R⁴,such as an ethoxy group derived from an ethyl group, etc.

Examples of the titanium compound represented by the above formula [I]are tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium,tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium,n-butoxytitanium trichloride, di-n-butoxytitanium dichloride,tri-n-butoxytitanium chloride, di-n-tetraisopropylpolytitanate which isa mixture of compounds having “a” of 2 to 10 in the above formula [I],tetra-n-butylpolytitanate which is a mixture of compounds having “a” of2 to 10 in the above formula [I], tetra-n-hexylpolytitanate which is amixture of compounds having “a” of 2 to 10 in the above formula [I], andtetra-n-octylpolytitanate which is a mixture of compounds having “a” of2 to 10 in the above formula [I], and a condensate obtained by reactingtetraalkoxytitanium with a small amount of water. Among them, preferredis a titanium compound having “a” of 1, 2 or 4 in the above formula [I],and particularly preferred is tetra-n-butoxytitanium,tetra-n-butyltitanium dimer, or tetra-n-butyltitanium tetramer. Thosetitanium compounds may be used in a combination of two or more thereof.

Examples of the above organosilicon compound are those represented bythe following respective formulas:

Si(OR⁵)_(t)R⁶ _(4-t),

R⁷(R⁸ ₂SiO)_(u)SiR⁹ ₃, and

(R¹⁰ ₂SiO)_(v),

wherein R⁵ is a hydrocarbyl group having 1 to 20 carbon atoms; R⁶, R⁷,R⁸, R⁹ and R¹⁰ are independently of one another a hydrocarbyl grouphaving 1 to 20 carbon atoms, or a hydrogen atom; t is an integersatisfying 0<t≦4; u is an integer of 1 to 1,000; and v is an integer of2 to 1,000.

Examples of the organosilicon compound are tetramethoxysilane,dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane,diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane,diisopropoxydiisopropylsilane, tetrapropoxysilane,dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane,dicyclopentoxydiethylsilane, diethoxydiphenylsilane,cyclohexyloxytrimethylsilane, phenoxytrimethylsilane,tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane,hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane,dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane andphenylhydropolysiloxane.

Among them, preferred is an alkoxysilane compound represented by theabove formula, Si(OR⁵)_(t)R⁶ _(4-t), wherein t is preferably an integersatisfying 1≦t≦4, and more preferably 4 (namely, tetraalkoxysilanecompound). Tetraethoxysilane is the most preferable compound.

The above organomagnesium compound may be any compound containing amagnesium-carbon bond therein. The organomagnesium compound ispreferably a Grignard compound represented by the following firstformula, or a dihydrocarbylmagnesium represented by the following secondformula:

R¹¹MgX³, and

R¹²R¹³Mg,

wherein R¹¹ is a hydrocarbyl group having 1 to 20 carbon atoms; X³ is ahalogen atom; and R¹² and R¹³ are independently of each other ahydrocarbyl group having 1 to 20 carbon atoms. Among them, morepreferred is a Grignard compound, and particularly preferred is asolution of a Grignard compound in an ether, in order to obtain apolymerization catalyst having a good shape.

Examples of R¹¹, R¹² and R¹³ are an alkyl group having 1 to 20 carbonatoms, an aryl group, an aralkyl group and an alkenyl group, such as amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, a sec-butyl group, a tert-butyl group, an isoamyl group, ahexyl group, an octyl group, a 2-ethylhexyl group, a phenyl group and abenzyl group.

The organomagnesium compound may be used as its complex soluble in ahydrocarbon solvent, which complex can be obtained by reacting theorganomagnesium compound with an organometal compound such as that ofLi, Be, B, Al or Zn.

Examples of the above ester compound are monocarboxylic acid esters andpolycarboxylic acid esters. Among them, preferred are unsaturatedaliphatic carboxylic acid esters such as methacrylic acid esters andmaleic acid esters, or aromatic carboxylic acid esters such as phthalicacid esters, and particularly preferred are phthalic acid dialkylesters. Specific examples thereof are saturated aliphatic carboxylicacid esters, unsaturated aliphatic carboxylic acid esters, alicycliccarboxylic acid esters, and aromatic carboxylic acid esters. Morespecific examples thereof are methyl acetate, ethyl acetate, phenylacetate, methyl propionate, ethyl propionate, ethyl butyrate, ethylvalerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butylbenzoate, methyl toluate, ethyl toluate, ethyl anisate, diethylsuccinate, dibutyl succinate, diethyl malonate, dibutyl malonate,dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate,monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethylphthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butylphthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexylphthalate, di-n-heptyl phthalate, di-n-octyl phthalate, di(2-ethylhexyl)phthalate, diisodecyl phthalate, dicyclohexyl phthalate and diphenylphthalate.

Each of the above organosilicon compound, titanium compound and estercompound is preferably combined with a solvent. Examples of the solventare aliphatic hydrocarbons such as hexane, heptane, octane and decane;aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbonssuch as cyclohexane, methylcyclohexane and decalin; and ether compoundssuch as diethyl ether, di-n-butyl ether, diisoamyl ether andtetrahydrofuran.

A temperature of the above reduction reaction is usually −50 to 70° C.,preferably −30 to 50° C., and particularly preferably −25 to 35° C. Atime thereof is not particularly limited, and it is usually about 30minutes to about 6 hours. The reduction reaction may be followed byheating at 0 to 120° C.

The solid material prepared in the above reduction reaction may besupported on a carrier such as a porous inorganic oxide and a porousorganic polymer. The carrier may be known in the art. Examples of thecarrier are inorganic oxides such as SiO₂, Al₂O₃, MgO, TiO₂ and ZrO₂;and polymers such as polystyrene, a styrene-divinylbenzene copolymer, astyrene-ethylene glycol dimethacrylate copolymer, polymethyl acrylate,polyethyl acrylate, a methyl acrylate-divinylbenzene copolymer,polymethyl methacrylate, a methyl methacrylate-divinylbenzene copolymer,polyacrylonitrile, an acrylonitrile-divinylbenzene copolymer, polyvinylchloride, polyethylene and polypropylene. Among them, preferred is anorganic polymer, and particularly preferred is a styrene-divinylbenzenecopolymer or an acrylonitrile-divinylbenzene copolymer.

In order to support effectively the solid material on a carrier, thecarrier has a pore volume of preferably 0.3 cm³/g or more, and morepreferably 0.4 cm³/g or more, in a pore radius of 20 to 200 nm. A ratioof the above pore volume is preferably 35% or more, and more preferably40% or more, provided that a pore volume in a pore radius of 3.5 to7,500 nm is 100%.

The above organosilicon compound is used in an amount of usually 1 to500 mol, preferably 1 to 300 mol, and particularly preferably 3 to 100mol, in terms of an amount of silicon atoms contained in theorganosilicon compound, per mol of titanium atoms contained in thetitanium compound used.

The above organomagnesium compound is used in an amount of usually 0.1to 10 mol, preferably 0.2 to 5.0 mol, and particularly preferably 0.5 to2.0 mol in terms of the amount of magnesium atoms contained in theorganomagnesium compound used, per mol of the total of the amount ofsilicon atoms contained in the organosilicon compound used, and theamount of titanium atoms contained in the titanium compound used.

Also, the organosilicon compound, the titanium compound and theorganomagnesium compound are respectively used such that a solidcatalyst component contains magnesium atoms in an amount of usually 1 to51 mol, preferably 2 to 31 mol, and particularly preferably 4 to 26 mol,per mol of titanium atoms contained in the solid catalyst component.

The above ester compound is used in an amount of usually 0.05 to 100mol, preferably 0.1 to 60 mol, and particularly preferably 0.2 to 30mol, per mol of titanium atoms contained in the titanium compound used.

The solid material obtained by the above reduction reaction is usuallyseparated from a reaction mixture, and then, is washed several timeswith an inert hydrocarbon solvent such as hexane, heptane and toluene.The thus obtained solid material contains trivalent titanium atoms,magnesium atoms and hydrocarbyloxy groups. The solid material generallyhas an amorphous structure, or a very weak crystalline structure, andthe former structure is particularly preferred.

The halogenation compound used in the above step (1) means a compoundcapable of replacing the hydrocarbyloxy group contained in the solidmaterial with a halogen atom. The halogenation compound is preferably ahalogen compound of Group 4, 13 or 14 elements in the Periodic Table ofthe elements, and more preferably a halogen compound of Group 4 or 14elements. When the solid material contains no titanium atom, at least ahalogen compound of a titanium atom is used as the halogenationcompound.

The above halogen compound of Group 4 elements is preferably a compoundrepresented by the following formula:

M¹(OR¹⁴)_(b)X⁴ _(4-b)

wherein M¹ is an atom of Group 4; R¹⁴ is a hydrocarbyl group having 1 to20 carbon atoms, and when plural R¹⁴s exist, they are the same as, ordifferent from one another; X⁴ is a halogen atom; and b is a numbersatisfying 0≦b<4, preferably 0≦b≦2, and particularly preferably b=0.

Examples of the above M¹ are a titanium atom, a zirconium atom and ahafnium atom. Among them, preferred is a titanium atom.

Examples of the above R¹⁴ are an alkyl group such as a methyl group, anethyl group, a propyl group, an isopropyl group, a butyl group, anisobutyl group, a tert-butyl group, an amyl group, an isoamyl group, atert-amyl group, a hexyl group, a heptyl group, an octyl group, a decylgroup and a dodecyl group; an aryl group such as a phenyl group, acresyl group, a xylyl group and a naphthyl group; an allyl group such asa propenyl group; and an aralkyl group such as a benzyl group. Amongthem, preferred is an alkyl group having 2 to 18 carbon atoms, or anaryl group having 6 to 18 carbon atoms, and particularly preferred is alinear alkyl group having 2 to 18 carbon atoms.

Examples of X⁴ are a chlorine atom, a bromine atom and an iodine atom.Among them, particularly preferred is a chlorine atom.

Examples of the halogen compound of Group 4 elements represented by theabove formula are a titanium tetrahalide such as titanium tetrachloride,titanium tetrabromide and titanium tetraiodide; an alkoxytitaniumtrihalide such as methoxytitanium trichloride, ethoxytitaniumtrichloride, butoxytitanium trichloride, phenoxytitanium trichloride andethoxytitanium tribromide; and a dialkoxytitanium dihalide such asdimethoxytitanium dichloride, diethoxytitanium dichloride,dibutoxytitanium dichloride, diphenoxytitanium dichloride anddiethoxytitanium dibromide; and hafnium compounds obtained by replacingthe titanium atom contained in the above-exemplified titanium compoundswith a hafnium atom. Among them, most preferred is titaniumtetrachloride.

The above halogen compound of Group 13 or 14 elements is preferably acompound represented by the following formula:

M²R¹⁵ _(m-c)X⁵ _(c)

wherein M² is an atom of Group 13 or 14; R¹⁵ is a hydrocarbyl grouphaving 1 to 20 carbon atoms; X⁵ is a halogen atom; m is the valence ofM²; and c is a number satisfying 0<c≦m.

Examples of the atom of Group 13 are a boron atom, an aluminum atom, agallium atom, an indium atom and a thallium atom. Among them, preferredis a boron atom or an aluminum atom, and more preferred is an aluminumatom.

Examples of the atom of Group 14 are a carbon atom, a silicon atom, agermanium atom, a tin atom and a lead atom. Among them, preferred is asilicon atom, a germanium atom or a tin atom, and more preferred is asilicon atom or a tin atom.

For example, when M² is a silicon atom, m is 4, and c is preferably 3 or4.

Examples of X⁵ are a fluorine atom, a chlorine atom, a bromine atom andan iodine atom. Among them, preferred is a chlorine atom.

Examples of the above R¹⁵ are an alkyl group such as a methyl group, anethyl group, a n-propyl group, an isopropyl group, a n-butyl group, anisobutyl group, an amyl group, an isoamyl group, a hexyl group, a heptylgroup, an octyl group, a decyl group and a dodecyl group; an aryl groupsuch as a phenyl group, a tolyl group, a cresyl group, a xylyl group anda naphthyl group; a cycloalkyl group such as a cyclohexyl group and acyclopentyl group; an allyl group such as a propenyl group; and anaralkyl group such as a benzyl group. Among them, preferred is an alkylgroup or an aryl group; and more preferred is a methyl group, an ethylgroup, a n-propyl group, a phenyl group or a p-tolyl group.

Examples of the above halogen compound of Group 13 elements aretrichloroborane, methyldichloroborane, ethyldichloroborane,phenyldichloroborane, cyclohexyldichloroborane, dimethylchloroborane,methylethylchloroborane, trichloroaluminum, methyldichloroaluminum,ethyldichloroaluminum, phenyldichloroaluminum,cyclohexyldichloroaluminum, dimethylchloroaluminum,diethylchloroaluminum, methylethylchloroaluminum, ethylaluminumsesquichloride, gallium chloride, gallium dichloride, trichlorogallium,methyldichlorogallium, ethyldichlorogallium, phenyldichlorogallium,cyclohexyldichlorogallium, dimethylchlorogallium,methylethylchlorogallium, indium chloride, indium trichloride,methylindium dichloride, phenylindium dichloride, dimethylindiumchloride, thallium chloride, thallium trichloride, methylthalliumdichloride, phenylthallium dichloride and dimethylthallium chloride; andcompounds obtained by replacing the chlorine atom contained in theabove-exemplified compounds with a fluorine atom, a bromine atom or aniodine atom.

Examples of the above halogen compound of Group 14 elements aretetrachloromethane, trichloromethane, dichloromethane,monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane,1,2-dichloroethane, 1,1,2,2-tetrachloroethane, tetrachlorosilane,trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane,n-propyltrichlorosilane, n-butyltrichlorosilane, phenyltrichlorosilane,benzyltrichlorosilane, p-tolyltrichlorosilane,cyclohexyltrichlorosilane, dichlorosilane, methyldichlorosilane,ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane,methylethyldichlorosilane, monochlorosilane, trimethylchlorosilane,triphenylchlorosilane, tetrachlorogermane, trichlorogermane,methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane,dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane,diphenyldichlorogermane, monochlorogermane, trimethylchlorogermane,triethylchlorogermane, tri-n-butylchlorogermane, tetrachlorotin,methyltrichlorotin, n-butyltrichlorotin, dimethyldichlorotin,di-n-butyldichlorotin, di-isobutyldichlorotin, diphenyldichlorotin,divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin,dichlorolead, methylchlorolead and phenylchlorolead; and compoundsobtained by replacing the chlorine atom contained in theabove-exemplified compounds with a fluorine atom, a bromine atom or aniodine atom. Among them, preferred is tetrachlorosilane,methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane,n-butyltrichlorosilane, phenyltrichlorosilane, tetrachlorotin,methyltrichlorotin or n-butyltrichlorotin.

The halogenation compound is preferably titanium tetrachloride,methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane,phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane,n-propyltrichlorosilane or tetrachlorotin, or a combination of two ormore thereof, and particularly preferably titanium tetrachloride ortetrachlorosilane, from a viewpoint of an activity of a polymerizationcatalyst.

Use of the above internal electron donor in the step (1) may improve anactivity or copolymerizability of a polymerization catalyst in thepresent invention. Examples of the internal electron donor areoxygen-containing electron donors such as ethers, ketones, aldehydes,carboxylic acids, organic acid esters, inorganic acid esters, organicacid amides, inorganic acid amides and acid anhydrides; andnitrogen-containing electron donors such as ammonia, amines, nitrilesand isocyanates. Among them, preferred are organic acid esters and/orethers, and more preferred are carboxylic acid esters and/or ethers.

Examples of the above carboxylic acid esters of the internal electrondonor are monocarboxylic acid esters and polycarboxylic acid esters.More specific examples thereof are saturated aliphatic monocarboxylicacid esters, saturated aliphatic polycarboxylic acid esters, unsaturatedaliphatic monocarboxylic acid esters, unsaturated aliphaticpolycarboxylic acid esters, alicyclic monocarboxylic acid esters,alicyclic polycarboxylic acid esters, aromatic monocarboxylic acidesters, and aromatic polycarboxylic acid esters. Preferred areunsaturated aliphatic carboxylic acid esters such as methacrylic acidesters and maleic acid esters, or aromatic carboxylic acid esters suchas benzoic acid esters and phthalic acid esters. Specific examplesthereof are methyl acetate, ethyl acetate, phenyl acetate, methylpropionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethylacrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyltoluate, ethyl toluate, ethyl anisate, diethyl succinate, dibutylsuccinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutylmaleate, diethyl itaconate, dibutyl itaconate, and phthalic acid estersrepresented by the following formula [II]:

wherein R¹⁶, R¹⁷, R¹⁸ and R¹⁹ are independently of one another ahydrogen atom or a hydrocarbyl group; and X⁶ and X⁷ are independently ofeach other a group consisting of hydrogen atoms and carbon atoms, or agroup consisting of hydrogen atoms, carbon atoms and one or more oxygenatoms contained in ether bonds.

R¹⁶, R¹⁷, R¹⁸ and R¹⁹ are preferably a hydrogen atom or a hydrocarbylgroup having 1 to 10 carbon atoms, and two or more hydrocarbyl groups ofR¹⁶, R¹⁷, R¹⁸ and R¹⁹ may be linked to one another to form a ring; X⁶and X⁷ are preferably a hydroxyl group or an alkoxy group having 1 to 20carbon atoms; and when an aromatic ring exits other than the R¹⁶-R¹⁹carrying-benzene ring, the aromatic ring may be partially or totallyhydrogenated.

The phthalic acid derivatives represented by the above formula arepreferably phthalic acid dialkyl esters; and particularly preferablyphthalic acid dialkyl esters, whose two alkyl groups have 8 or lesscarbon atoms in total. Examples of the phthalic acid derivatives aredimethyl phthalate, methyl ethyl phthalate, diethyl phthalate,di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate,diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate,di-n-heptyl phthalate, diisoheptyl phthalate, di-n-octyl phthalate,di(2-ethylhexyl) phthalate, di-n-decyl phthalate, diisodecyl phthalate,dicyclohexyl phthalate, diphenyl phthalate, and phthalic dichloride, anda combination of two or more thereof. Among them, preferred is diethylphthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butylphthalate, or diisobutyl phthalate.

Examples of the above ethers of the internal electron donor are dialkyethers, cyclic ethers which are heterocyclic compounds having at leastone ether bond (—C—O—C—) in their rings, and 1,3-diethers.

Examples of the above dialky ethers are dimethyl ether, diethyl ether,di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutylether, methyl-n-propyl ether, methyl-n-butyl ether, ethyl-n-propylether, ethyl-n-butyl ether, and methyl cyclohexyl ether. Among them,preferred is di-n-butyl ether, which is hereinafter referred to as“dibutyl ether” or “butyl ether”.

Examples of the above cyclic ethers are ethylene oxide, propylene oxide,trimethylene oxide, tetrahydrofuran, 2,5-dimethoxytetrahydrofuran,tetrahydropyrane, hexamethylene oxide, 1,3-dioxepane, 1,3-dioxane,1,4-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane,2,2-dimethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane,2,4-dimethyl-1,3-dioxolane, furan, 2,5-dimethylfuran and s-trioxane.Among them, preferred are cyclic ethers containing at least one—C—O—C—O—C— bond in their rings.

Examples of the above 1,3-diethers are those represented by thefollowing formula [III]:

wherein R²⁰, R²¹, R²² and R²³ are independently of one another a C₁₋₂₀linear alkyl group, a branched alkyl group, an alicyclic alkyl group, anaryl group or an aralkyl group, and R²⁰ and R²¹ may be independently ofeach other a hydrogen atom, and may be linked to each other to form aring.

Examples of the 1,3-diethers represented by the above formula [III] are2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane,2,2-diisopropyl-1,3-dimethoxypropane,2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane,2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane,2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-dicyclopentyl-1,3-dimethoxypropane, and2-heptyl-2-pentyl-1,3-dimethoxypropane, and a combination of two or morethereof.

The organic acid halide used in the step (1) is preferablymonocarboxylic acid halides or polycarboxylic acid halides. Examplesthereof are aliphatic carboxylic acid halides, alicyclic carboxylic acidhalides, and aromatic carboxylic acid halides. Specific examples thereofare acetyl chloride, propionic acid chloride, butylic acid chloride,valeric acid chloride, acrylic acid chloride, methacrylic acid chloride,benzoic acid chloride, toluic acid chloride, anisic acid chloride,succinic acid chloride, malonic acid chloride, maleic acid chloride,itaconic acid chloride, and phthalic acid chloride. Among them,preferred are aromatic monocarboxylic acid chlorides such as benzoicacid chloride and toluic acid chloride, or aromatic dicarboxylic aciddichlorides such as phthalic acid dichloride, further preferred arearomatic dicarboxylic acid dichlorides, and particularly preferred isphthalic acid dichloride.

The step (1) is carried out usually in an atmosphere of an inert gassuch as nitrogen and argon. Examples of an order of contacting the solidmaterial with the halogenation compound and the internal electron donorand/or organic acid halide are the following (1) to (10):

(1) adding a halogenation compound and an internal electron donor to asolid material in an optional order;

(2) adding a halogenation compound and an organic acid halide to a solidmaterial in an optional order;

(3) adding a mixture of a halogenation compound, an internal electrondonor and an organic acid halide to a solid material;

(4) adding a mixture of a halogenation compound and an internal electrondonor, and an organic acid halide, in an optional order, to a solidmaterial;

(5) adding an internal electron donor to a solid material, and then,adding a halogenation compound thereto;

(6) adding an internal electron donor to a solid material, and then,adding a halogenation compound and an internal electron donor thereto,in an optional order, wherein the former internal electron donor or thelatter internal electron donor is additionally added;

(7) adding an internal electron donor to a solid material, and then,adding a mixture of a halogenation compound and an internal electrondonor thereto, wherein the former internal electron donor or the latterinternal electron donor is additionally added;

(8) adding a solid material and an internal electron donor to ahalogenation compound in an optional order;

(9) adding a solid material and an organic acid halide to a halogenationcompound in an optional order; and

(10) adding a solid material, an internal electron donor and an organicacid halide to a halogenation compound in an optional order.

The above orders (1) to (10) may be followed by one or more steps ofadding a halogenation compound or a mixture of a halogenation compoundand an internal electron donor.

Among them, preferred is the order (2); the order (4); the order (4)followed by one or more steps of adding a mixture of a halogenationcompound and an internal electron donor; or the order (7), wherein thesecond step of adding a mixture of a halogenation compound and aninternal electron donor may be repeated. More preferred is the order(4); the order (4) followed by one or more steps of adding a mixture ofa halogenation compound and an internal electron donor; or the order(7), wherein the second step of adding a mixture of a halogenationcompound and an internal electron donor may be repeated. Particularlypreferred is the order (4) using an ether as an internal electron donor,followed by the step of adding a mixture of a halogenation compound andan internal electron donor, wherein the internal electron donor is acombination of a carboxylic acid ester and an ether, and furtherfollowed by one or more steps of adding a mixture of a halogenationcompound and an internal electron donor, wherein the internal electrondonor is an ether; or the order (7) using a carboxylic acid ester as thefirst internal electron donor, and using a combination of a carboxylicacid ester with an ether as the second internal electron donor, followedby one or more steps of adding a mixture of a halogenation compound andan internal electron donor, wherein the internal electron donor is anether.

A method for contacting the solid material, the halogenation compound,the internal electron donor and/or organic acid halide with one anotheris not particularly limited. Examples of the method are conventionalmethods such as a slurry method, and a mechanically pulverizing methodusing a ball mill. The mechanically pulverizing method is preferablycarried out in the presence of a diluent, in order to suppressproduction of fine powders, thereby obtaining a solid component having anarrow particle size distribution.

The above diluent is preferably inert to the solid material, thehalogenation compound, the internal electron donor and the organic acidhalide. Examples of the diluent are aliphatic hydrocarbons such aspentane, hexane, heptane and octane; aromatic hydrocarbons such asbenzene, toluene and xylene; licyclic hydrocarbons such as cyclohexaneand cyclopentane; and halogenated hydrocarbons such as1,2-dichloroethane and monochlorobenzene. Among them, preferred arealiphatic hydrocarbons or aromatic hydrocarbons, more preferred arearomatic hydrocarbons, and further preferred is toluene or xylene.

The above diluent is used in an amount of usually 0.1 to 1,000 mL, andpreferably 1 to 100 mL, per one g of the solid material, per onecontact.

A time for the above contact is not particularly limited, and ispreferably 0.5 to 8 hours, and more preferably 1 to 6 hours. Itstemperature is usually −50 to 150° C., preferably 0 to 140° C., andfurther preferably 60 to 135° C.

The above contact is carried out preferably under agitation, in order tomaintain a homogeneous slurry state. Too week agitation may result ininsufficient contact, and therefore, the finally obtained polymerizationcatalyst may be insufficient in its stereoregularity or activity. Toostrong agitation may break the solid component obtained.

The halogenation compound is used in an amount of usually 0.5 to 1.000mmol, preferably 1 to 200 mmol, and further preferably 2 to 100 mmol,per one gram of the solid material. The halogenation compound is usedpreferably in combination with the internal electron donor, which isused in an amount of usually 1 to 100 mol, preferably 1.5 to 75 mol, andfurther preferably 2 to 50 mol, per one mol of the halogenationcompound.

The internal electron donor is used in an amount of usually 0.01 to 100mmol, preferably 0.05 to 50 mmol, and further preferably 0.1 to 20 mmol,per one gram of the solid material.

The organic acid halide is used in an amount of usually 0.1 to 100 mmol,preferably 0.3 to 50 mmol, and further preferably 0.5 to 20 mmol, perone gram of the solid material, and is used in an amount of usually 0.01to 1.0 mol, and preferably 0.03 to 0.5 mol, per one mol of magnesiumatoms contained in the solid material.

When the internal electron donor or organic acid halide is used in anamount of larger than 100 mmol per one gram of the solid material, theobtained solid component having a particulate form may be broken.

Regarding the Step (2):

The step (2) washes away from the solid component such compounds astitanium compounds unfavorable in view of the object of the presentinvention.

Examples of the hydrocarbon solvent used in the step (2) are aliphatichydrocarbons such as pentane, hexane, heptane, octane and decane; andaromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene andxylene. Among them, preferred is an aromatic hydrocarbon, and morepreferred is toluene or xylene.

Examples of the hydrocarbon solvent used in the step (2) are aromatichydrocarbon solvents such as benzene, toluene, ethylbenzene and xylene.Among them, preferred is toluene or xylene.

The hydrocarbon solvent is used in an amount of usually 0.1 to 1,000 mL,and preferably 1 to 100 mL, per one g of the solid component, per onewashing.

A washing temperature in the step (2) is usually −50 to 150° C.,preferably 0 to 140° C., and further preferably 60 to 135° C. A washingtime therein is not particularly limited, and is preferably 1 to 120minutes, more preferably 2 to 60 minutes, and further preferably 5 to 40minutes. The number of the washing is usually one to five times, and sixor more times if needed.

The washing is carried out preferably under agitation, in order tomaintain a homogeneous slurry state. Too week agitation may result ininsufficient washing, and therefore, the finally obtained polymerizationcatalyst may be insufficient in its stereoregularity or activity. Toostrong agitation may break the solid component.

Regarding the Step (3):

Contact conditions in the step (3) are the same as those in the step(1), except that the solid material in the step (1) is replaced with thewashed solid component.

Regarding the Step (4):

Examples of the hydrocarbon solvent used in the step (4) are aliphatichydrocarbons such as pentane, hexane, heptane, octane and decane;aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene.Among them, preferred is an aromatic hydrocarbon, and more preferred istoluene or xylene.

An amount of the hydrocarbon solvent used for washing, and a washingtime are similar to those in the step (2) mentioned above.

A washing temperature is 70° C. or higher, generally 70 to 150° C.,preferably 90 to 140° C., and more preferably 100 to 135° C.

A washing is carried out four or more times, preferably five or moretimes, and more preferably six or more times.

The step (4) washes away from the solid component such compounds astitanium compounds unfavorable in view of the object of the presentinvention, more strongly than the step (2), to the extent that thefollowing filtrate contains titanium atoms in a concentration of 0.08mg-Ti/ml-filtrate or lower, measured according to a method comprisingthe steps of:

(1) preparing a suspension of the finally-obtained solid catalystcomponent for olefin polymerization in heptane having a concentration of0.1 g-solid catalyst component/ml-suspension;

(2) heating the suspension at 70° C. for 30 minutes under stirring;

(3) filtering the suspension using, for example, a G4 filter, therebyobtaining a filtrate; and

(4) measuring a concentration of titanium atoms contained in thefiltrate, according to an analytical method known in the art such as anUV-optical density method and an ICP emission method.

The solid catalyst component for olefin polymerization in the presentinvention contains preferably chlorine atoms as the halogen atoms, andcontains preferably ethoxy groups and/or butoxy groups as thehydrocarbyloxy groups.

The solid catalyst component for olefin polymerization in the presentinvention comprises titanium atoms in an amount of 0.1 to 3.0% by weightand preferably 0.5 to 2.5% by weight, magnesium atoms in an amount of 5to 30% by weight and preferably 10 to 25% by weight, halogen atoms in anamount of 40 to 70% by weight and preferably 45 to 65% by weight, andhydrocarbyloxy groups in an amount of 0.1 to 3.5% by weight andpreferably 0.5 to 3.0% by weight, the total weight of the solid catalystcomponent being 100% by weight.

The solid catalyst component for olefin polymerization may be used forpolymerization in a form of its slurry in an inert solvent, or may beused for polymerization in a form of its fluid dry powder. Examples of adrying method for obtaining the fluid dry powder are a reduced-pressuredrying method, and a method comprising the step of removing volatilematters contained in the solid catalyst component under a flow of aninert gas such as nitrogen and argon. The drying is carried out atpreferably 0 to 200° C., and more preferably 50 to 100° C., and forpreferably 0.01 to 20 hours, and more preferably 0.5 to 10 hours.

The organoaluminum compound used in the present invention is a compoundhaving one or more aluminum-carbon bonds in its molecule, and may be acompound known in the art. Examples thereof are compounds represented bythe following formulas, respectively:

R²⁴ _(w)AlX⁸ _(3-w), and

R²⁵R²⁶Al—O—AlR²⁷R²⁸,

wherein R²⁴ to R²⁸ are independently of one another a hydrocarbyl grouphaving 1 to 20 carbon atoms; X⁸ is a halogen atom, a hydrogen atom or analkoxy group; and w is a number satisfying 2≦w≦3.

Examples of the organoaluminum compound are trialkylaluminums such astriethylaluminum, triisobutylaluminum and trihexylaluminum;dialkylaluminum hydrides such as diethylaluminum hydride anddiisobutylaluminum hydride; dialkylaluminum halides such asdiethylaluminum chloride; mixtures of trialkylaluminums anddialkylaluminum halides such as a mixture of triethylaluminum anddiethylaluminum chloride; and alkylalumoxanes such astetraethyldialumoxane and tetrabutyldialumoxane. Among them, preferredare trialkylaluminums, mixtures of trialkylaluminums withdialkylaluminum halides, or alkylalumoxanes; and particularly preferredis triethylaluminum, triisobutylaluminum, a mixture of triethylaluminumwith diethylaluminum chloride, or tetraethyldialumoxane.

Examples of the external electron donor used in the present inventionare oxygen-containing compounds, nitrogen-containing compounds,phosphorus-containing compounds and sulfur-containing compounds. Amongthem, preferred are oxygen-containing compounds or nitrogen-containingcompounds.

Examples of the oxygen-containing compounds are alkoxysilicon compounds,ethers, esters and ketones. Among them, preferred are alkoxysiliconcompounds or ethers.

Examples of the alkoxysilicon compounds are compounds represented by thefollowing formula:

R²⁹ _(r)Si(OR³⁰)_(4-r)

wherein R²⁹ is a hydrocarbyl group having 1 to 20 carbon atoms, ahydrogen atom, or a hetero atom-containing group, and when plural R²⁹sexist, they are the same as, or different from one another; R³⁰ is ahydrocarbyl group having 1 to 20 carbon atoms, and when plural R³⁰sexist, they are the same as, or different from one another; and r is anumber satisfying 0≦r<4.

Examples of the above hydrocarbyl group of R²⁹ are a linear alkyl groupsuch as a methyl group, an ethyl group, a propyl group, a butyl groupand a pentyl group; a branched-chain alkyl group such as an isopropylgroup, a sec-butyl group, a tert-butyl group and a tert-amyl group; acycloalkyl group such as a cyclopentyl group and a cyclohexyl group; acycloalkenyl group such as a cyclopentenyl group; and an aryl group suchas a pheny group and a tolyl group.

The compounds represented by the above formula are preferably compoundshaving at least one hydrocarbyl group of R²⁹, which contains a secondaryor tertiary carbon atom linked to the silicon atom.

Examples of the hetero atom contained in the above heteroatom-containing group of R²⁹ are an oxygen atom, a nitrogen atom, asulfur atom and a phosphorus atom. Examples of the heteroatom-containing group area dimethylamino group, a methylethylaminogroup, a diethylamino group, an ethyl-n-propylamino group, adi-n-propylamino group, a pyrrolyl group, a pyridyl group, apyrrolidinyl group, a piperidyl group, a perhydroindolyl group, aperhydroisoindolyl group, a perhydroquinolyl group, aperhydroisoquinolyl group, a perhydrocarbazolyl group, aperhydroacridinyl group, a furyl group, a pyranyl group, a perhydrofurylgroup and a thienyl group. Among them, preferred are heteroatom-containing groups, whose hetero atom is directly linked to thesilicon atom.

Examples of the above alkoxysilicon compounds as the oxygen-containingcompounds are diisopropyldimethoxysilane, diisobutyldimethoxysilane,di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane,tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane,tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane,tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane,tert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane,tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane,cyclobutylisopropyldimethoxysilane, cyclobutylisobutyldimethoxysilane,cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane,cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane,cyclopentyl-tert-butyldimethoxysilane, dicylohexyldimethoxysilane,cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane,cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane,cyclohexyl-tert-butyldimethoxysilane,cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane,diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane,phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane,diisopropyldiethoxysilane, diisobutyldiethoxysilane,di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane,tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane,tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane,tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane,tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane,dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane,cyclohexylethyldiethoxysilane, diphenyldiethoxysilane,phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane,bis(perhydroquinolino)dimethoxysilane,bis(perhydroisoquinolino)dimethoxysilane,(perhydroquinolino)(perhydroisoquinolino)dimethoxysilane,(perhydroquinolino)methyldimethoxysilane,(perhydroisoquinolino)methyldimethoxysilane,(perhydroquinolino)ethyldimethoxysilane,(perhydroisoquinolino)ethyldimethoxysilane,(perhydroquinolino)(n-propyl)dimethoxysilane,(perhydroisoquinolino)(n-propyl)dimethoxysilane,(perhydroquinolino)(tert-butyl)dimethoxysilane,(perhydroisoquinolino)(tert-butyl)dimethoxysilane,diethylaminodimethoxysilane, and diethylaminodiethoxysilane.

Examples of the ethers of the above oxygen-containing compounds arethose exemplified above as the cyclic ethers or the 1,3-diethers of theinternal electron donor.

Examples of the nitrogen-containing compounds of the above externalelectron donor are 2,6-substituted piperidines such as2,6-dimethylpiperidine and 2,2,6,6-tetramethylpiperidine; substitutedmethylene diamines such as 2,5-substituted piperidines,N,N,N′,N′-tetramethylmethylene diamine and N,N,N′,N′-tetraethylmethylenediamine; and substituted imidazolidines such as1,3-dibenzylimidazolidine. Among them, preferred are 2,6-substitutedpiperidines.

The external electron donor is particularly preferablycyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane,diisopropyldimethoxysilane, tert-butylethyldimethoxysilane,tert-butyl-n-propyldimethoxysilane, phenyldimethoxysilane,diphenyldimethoxysilane, dicyclobutyldimethoxysilane,dicyclopentyldimethoxysilane, 1,3-dioxolane, 1,3-dioxane,2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane,2,2-diisopropyl-1,3-dimethoxypropane or2,2-dicyclohexyl-1,3-dimethoxypropane.

A method for contacting the solid catalyst component for olefinpolymerization with the organoaluminum compound and the externalelectron donor is not limited. Examples of the method are (1) a methodcomprising the steps of (1-1) contacting the solid catalyst componentwith the organoaluminum compound and the external electron donor in thepresence or absence of a solvent, and then (1-2) feeding the obtainedmixture to a polymerization reactor, (2) a method comprising the step offeeding the solid catalyst component, the organoaluminum compound andthe external electron donor separately to a polymerization reactor,thereby contacting those components with one another in thepolymerization reactor, and (3) a method comprising the steps of (3-1)contacting any two of the solid catalyst component, the organoaluminumcompound and the external electron donor with each other, therebyobtaining a mixture, and (3-2) feeding the mixture and the remainingcomponent to a polymerization reactor, thereby contacting them with eachother in the polymerization reactor. The above feeding to apolymerization reactor is carried out preferably in a water-free stateand in an atmosphere of an inert gas such as nitrogen and argon.

The olefin in the present invention means ethylene or α-olefins havingthree or more carbon atoms. Examples of the α-olefins are linearmono-olefins such as propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene and 1-decene; branched mono-olefins such as3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene; andvinylcyclohexane. Those olefins may be used in combination of two ormore thereof, and may be used in combination with monomers containingplural unsaturated bonds such as conjugated dienes and non-conjugateddienes.

The olefin polymer in the present invention is preferably a propylenehomopolymer, a 1-butene homopolymer, a 1-pentene homopolymer, a 1-hexenehomopolymer, an ethylene-propylene copolymer, an ethylene-1-butenecopolymer, an ethylene-1-hexene copolymer, a propylene-1-butenecopolymer, a propylene-1-hexene copolymer, anethylene-propylene-1-butene copolymer, an ethylene-propylene-1-hexenecopolymer, or a hetero-block copolymer; more preferably a propylenehomopolymer or a propylene copolymer containing mainly propylene units;further preferably a propylene homopolymer or a propylene copolymercontaining 50% by weight or more of a propylene unit, the total of thepropylene copolymer being 100% by weight; and particularly preferably astereoregular propylene homopolymer. The above “hetero-block copolymer”means a mixture of two or more kinds of polymers, such as a mixture of apropylene homopolymer with an ethylene-propylene copolymer, which isproduced according to a process comprising the steps of (i)homopolymerizing propylene, thereby forming a propylene homopolymer, and(ii) copolymerizing ethylene with propylene in the presence of thepropylene homopolymer.

Stereoregularity of a propylene homopolymer or a propylene copolymercontaining mainly propylene units can be represented by an amount ofsoluble parts in xylene at 20° C. (CXS) of the homopolymer or thecopolymer. The smaller the CXS value is, the higher the stereoregularityis. A CXS of a propylene homopolymer is preferably 0.6% by weight orsmaller, and more preferably 0.5% by weight or smaller, the total of thepropylene homopolymer being 100% by weight.

Prior to polymerizing an olefin in the presence of the above catalystfor olefin polymerization, which is referred to as “realpolymerization”, the following “pre-polymerization” can be carried out.

The pre-polymerization is carried out using a combination of the abovesolid catalyst component for olefin polymerization with a monomer suchan olefin, in order to make a pre-polymerized catalyst component whosesurface is covered by a polymer such as a polyolefin formed bypre-polymerizing the monomer such as an olefin. The real polymerizationuses the solid catalyst component for olefin polymerization withoutmodification, or uses the above pre-polymerized catalyst component.

The pre-polymerized catalyst component is preferably produced by slurrypolymerization of a small amount of an olefin in the presence of theabove solid catalyst component for olefin polymerization andorganoaluminum compound. Examples of a solvent used for the slurrypolymerization are inert hydrocarbon solvents such as propane, butane,isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane,benzene and toluene. A partial or total amount of the inert hydrocarbonsolvents may be replaced with liquid olefins.

The organoaluminum compound in the pre-polymerization is used in anamount of usually 0.5 to 700 mol, preferably 0.8 to 500 mol, andparticularly preferably 1 to 200 mol, per one mol of titanium atomscontained in the solid catalyst component for olefin polymerizationused.

An amount of an olefin pre-polymerized is usually 0.01 to 1,000 g,preferably 0.05 to 500 g, and particularly preferably 0.1 to 200 g, per1 g of the solid catalyst component for olefin polymerization used.

A slurry concentration of the above slurry polymerization is preferably1 to 500 g-solid catalyst component/liter-solvent, and particularlypreferably 3 to 300 g-solid catalyst component/liter-solvent.

The pre-polymerization is carried out at preferably −20 to 100° C., andparticularly preferably 0 to 80° C. A partial pressure of an olefincontained in a gas phase of the pre-polymerization is preferably 1 kPato 2 MPa, and particularly preferably 10 kPa to 1 MPa, except an olefinhaving a liquid state under a pre-polymerization pressure andtemperature. A pre-polymerization time is not particularly limited, andis preferably 2 minutes to 15 hours.

Examples of a method for feeding the solid catalyst component, theorganoaluminum compound and an olefin to a pre-polymerization reactorare (1) a method comprising the steps of (1-1) feeding the solidcatalyst component and the organoaluminum compound, and then (1-2)feeding an olefin, and (2) a method comprising the steps of (2-1)feeding the solid catalyst component and an olefin, and then (2-2)feeding the organoaluminum compound. Examples of a method for feeding anolefin to a pre-polymerization reactor are (1) a method comprising thestep of feeding an olefin one after another while keeping an innerpressure of a pre-polymerization reactor at a predetermined pressure,and (2) a method comprising the step of feeding the predetermined totalamount of an olefin at the beginning. In order to control a molecularweight of an obtained pre-polymer, a chain transfer agent such ashydrogen may be added to a pre-polymerization reactor.

The pre-polymerization may use a partial or total amount of the externalelectron donor to be used in the above-mentioned production of thepolymerization catalyst. An amount of an external electron donor used inthe pre-polymerization is usually 0.01 to 400 mol, preferably 0.02 to200 mol, and particularly preferably 0.03 to 100 mol, per one mol oftitanium atoms contained in the solid catalyst component, or is usually0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably0.01 to 2 mol, per 1 mol of the organoaluminum compound used.

In the pre-polymerization, a method for feeding the organoaluminumcompound and the external electron donor to a pre-polymerization reactoris not particularly limited. Examples of the method are (1) a methodcomprising the step of feeding the external electron donor theretoseparately from the organoaluminum compound, and (2) a method comprisingthe steps of (i) contacting the external electron donor with theorganoaluminum compound, thereby forming a mixture, and then (ii)feeding the mixture to the pre-polymerization reactor. An olefin usedfor the pre-polymerization is the same as, or different from that usedfor the real polymerization.

The organoaluminum compound in the real polymerization is used in anamount of usually 1 to 1,000 mol, and particularly preferably 5 to 600mol, per one mol of titanium atoms contained in the solid catalystcomponent used.

The external electron donor in the real polymerization is used in anamount of usually 0.1 to 2,000 mol, preferably 0.3 to 1,000 mol, andparticularly preferably 0.5 to 800 mol, per one mol of titanium atomscontained in the solid catalyst component used, or is used in an amountof usually 0.001 to 5 mol, preferably 0.005 to 3 mol, and particularlypreferably 0.01 to 1 mol, per one mol of the organoaluminum compoundused.

The real polymerization is carried out:

(1) at usually −30 to 300° C., and preferably 20 to 180° C.;

(2) under a pressure, which is not particularly limited, of usually anatmospheric pressure to 10 MPa, and preferably 200 kPa to 5 MPa, from anindustrial and economical point of view;

(3) according to a batchwise method or a continuous method; and

(4) according to (4-1) a slurry or solution polymerization method withan inert hydrocarbon solvent such as propane, butane, isobutane,pentane, hexane, heptane and octane, (4-2) a bulk polymerization methodusing an olefin as a solvent, which olefin is liquid at a polymerizationtemperature, or (4-3) a gas-phase polymerization method.

The real polymerization may be a hetero-block copolymerization carriedout according to two or more polymerization steps.

In order to control a molecular weight of an olefin polymer produced, achain transfer agent such as hydrogen may be used.

According to the present invention, there can be provided (i) a solidcatalyst component for olefin polymerization capable of producing ahighly stereoregular olefin polymer, which can be molded into aninjection-molded article having superior stiffness, (ii) a process forproducing the above solid catalyst component (i), (iii) a process forproducing an olefin polymerization catalyst using the above solidcatalyst component (i); and (iv) a process for producing an olefinpolymer using an olefin polymerization catalyst produced according tothe above process (iii).

EXAMPLE

The present invention is explained in more detail with reference to thefollowing Examples, which do not limit the present invention.

Example 1 1. Preparation of a Solid Catalyst Component

A reactor equipped with a stirrer was purged with nitrogen gas, and then800 liters of hexane, 6.8 kg of diisobutyl phthalate, 350 kg oftetraethoxysilane and 38.8 kg of tetra-n-butoxytitanium were put intothe reactor. The resultant mixture was stirred. To the mixture, 900liters of a dibutyl ether solution (concentration: 2.1 mol/liter) ofbutylmagnesium chloride were added dropwise at 7° C. over 5 hours understirring. After completion of the dropwise addition, the mixture wasstirred at 20° C. for one hour. The obtained reaction mixture wasfiltered to separate a solid. The separated solid was washed three timesat room temperature with each 1,100 liters of toluene to obtain a washedsolid. Toluene was added to the washed solid, thereby obtaining 625liters of a toluene slurry of the solid. The toluene slurry was heatedat 70° C. for one hour under stirring, and then was cooled down to theroom temperature, thereby obtaining a toluene slurry of a solidmaterial.

A part of the toluene slurry was dried under a reduced pressure, therebyobtaining a dried solid material. The dried solid material was found tocontain 2.1% by weight of titanium atoms, 38.9% by weight of ethoxygroups, and 3.4% by weight of butoxy groups, the total weight of thedried solid material being 100% by weight, and the above titanium atomswere found to be trivalent.

Step (1):

A 100 mL-flask equipped with a stirrer, a dropping funnel and athermometer was purged with nitrogen gas. There was put into the flaskthe above solid material-containing toluene slurry, the total of thetoluene slurry used containing 8 g of the dried solid material.Supernatant toluene in the flask was taken out till the total volume ofthe toluene slurry was decreased to 26.5 mL. To the slurry, a mixture of16.0 mL of titanium tetrachloride with 0.8 mL of dibutyl ether was addedat 40° C., and further, a mixture of 2.0 mL of phthalic acid dichloridewith 2.0 mL of toluene was added dropwise over five minutes. Aftercompletion of the dropwise addition, the resultant reaction mixture wasstirred at 115° C. for four hours. The obtained reaction mixture wasfiltered at 115° C. to separate a solid component.

Step (2):

The above-separated solid component was washed three times at 115° C.with each 40 mL of toluene.

Step (3):

Toluene was added to the above-washed solid component, thereby obtaining26.5 mL of a toluene slurry. To the toluene slurry, a mixture of 0.8 mLof dibutyl ether, 0.45 mL of diisobutyl phthalate, and 6.4 mL oftitanium tetrachloride was added. The resultant mixture was stirred at105° C. for one hour. The obtained reaction mixture was filtered toseparate a solid component.

Step (2) Repeated:

The above-separated solid component was washed two times at 105° C. witheach 40 mL of toluene.

Step (3) Repeated:

Toluene was added to the above-washed solid component, thereby obtaining26.5 mL of a toluene slurry. To the toluene slurry, a mixture of 0.8 mLof dibutyl ether with 6.4 mL of titanium tetrachloride was added. Theresultant mixture was stirred at 105° C. for one hour. The obtainedreaction mixture was filtered to separate a solid component.

Step (2) Further Repeated:

The above-separated solid component was washed two times at 105° C. witheach 40 mL of toluene.

Step (3) Further Repeated:

Toluene was added to the above-washed solid component, thereby obtaining26.5 mL of a toluene slurry. To the toluene slurry, a mixture of 0.8 mLof dibutyl ether with 6.4 mL of titanium tetrachloride was added. Theresultant mixture was stirred at 105° C. for one hour. The obtainedreaction mixture was filtered to separate a solid component.

Step (4):

The above-separated solid component was washed six times at 105° C. witheach 40 mL of toluene, and was further washed three times at a roomtemperature with each 40 mL of hexane. The washed solid component wasdried under a reduced pressure, thereby obtaining a solid catalystcomponent for olefin polymerization.

The above-obtained solid catalyst component for olefin polymerizationwas found to contain 1.6% by weight of titanium atoms, 0.06% by weightof ethoxy groups, 0.15% by weight of butoxy groups, 7.6% by weight ofdiethyl phthalate, 0.8% by weight of ethyl-n-butyl phthalate, and 2.5%by weight of diisobutyl phthalate, the total weight of the solidcatalyst component being 100% by weight.

There was added 5.07 g of the above solid catalyst component for olefinpolymerization to 51 mL of heptane maintained at 70° C., therebypreparing a suspension of the solid catalyst component for olefinpolymerization in heptane having a concentration of 0.1 g-solid catalystcomponent/ml-suspension. The prepared suspension was stirred at 70° C.for 30 minutes, and was filtered with G4 filter. The obtained filtratewas found to contain titanium atoms in a concentration of 0.023 mg/ml,measured according to the following method comprising the steps of:

(1) putting 40 mL of the filtrate into a 50 mL measuring flask;

(2) evaporating the total amount of heptane contained in the filtratewith a nitrogen gas flow;

(3) decomposing the solid catalyst component with about 30 mL of 2normal (2 N) dilute sulfuric acid;

(4) adding 3 mL of hydrogen peroxide water having a concentration of 3%by weight, thereby preparing a liquid sample;

(5) measuring a characteristic absorption of the liquid sample at 410 nmwith a double-beam spectrophotometer, U-2001, manufactured by Hitachi,Ltd.; and

(6) finding a concentration of titanium atoms in the filtrate, based onthe characteristic absorption, with a calibration curve prepared inadvance.

2. Polymerization of Propylene

A stainless steel autoclave having a 3-liter inner volume was madevacuum, and hydrogen gas was added thereto till its partial pressurereached 0.15 MPa. There were put into the autoclave 7.81 mg of theabove-obtained solid catalyst component, 2.6 mmol of triethylaluminum(organoaluminum compound) and 0.52 mmol oftert-butyl-n-propyldimethoxysilane (external electron donor), and then780 g of liquid propylene was put therein. The autoclave was heated upto 70° C., and propylene was polymerized at 70° C. for one hour, therebyobtaining 319 g of a powdery propylene homopolymer.

A yield of the propylene homopolymer per one g of the solid catalystcomponent was 40,800 g/g. The propylene homopolymer had 0.48% by weightof soluble parts in xylene at 20° C. (CXS), the total weight of thepropylene homopolymer being 100% by weight; an intrinsic viscosity ([η])of 1.71 dl/g; and a bulk density of 0.448 g/mL.

The above titanium atom content (% by weight) was measured according toa method comprising the steps of:

(1) decomposing about 20 mg of a sample with about 30 mL of 2 normal (2N) dilute sulfuric acid;

(2) adding 3 mL (excess amount) of hydrogen peroxide water having aconcentration of 3% by weight, thereby preparing a liquid sample;

(3) measuring a characteristic absorption of the liquid sample at 410 nmwith a double-beam spectrophotometer, U-2001, manufactured by Hitachi,Ltd.; and

(4) finding a titanium atom content, based on the characteristicabsorption, with a calibration curve prepared in advance.

The above alkoxy group content (% by weight) was measured according to amethod comprising the steps of:

(1) decomposing about 2 g of a sample with 100 mL of water to obtain aliquid sample;

(2) measuring an amount of an alcohol (corresponding to an alkoxy group)contained in the liquid sample according to a gas chromatographyinternal standard method; and

(3) converting the obtained amount of an alcohol to an alkoxy groupcontent.

The above carboxylic acid ester content (% by weight) was measuredaccording to a method comprising the steps of:

(1) dissolving 30 mg of a sample in 100 mL of N,N-dimethylacetamide,thereby preparing a solution; and

(2) measuring a content of a carboxylic acid ester in the solutionaccording to a gas chromatography internal standard method.

The above valence of titanium atoms (trivalent titanium atoms) wasmeasured according to a method comprising the steps of:

(1) dissolving about 70 mg of a solid material in about 30 mL of anaqueous solution consisting of 240 mL of purified water, 113 g oftartaric acid and 260 mL of two normal (2 N) sulfuric acid, therebypreparing a solution; and

(2) measuring a valence of titanium atoms contained in the solution witha polarographic analyzer, P-1100, manufacture by Yanagimoto Corporationaccording to a DC (direct-current) electricity method.

The above amount of soluble parts in xylene at 20° C. (CXS) was measuredaccording to a method comprising the steps of:

(1) dissolving 1 g of a polymer in 200 mL of boiling xylene;

(2) cooling the solution gradually down to 50° C.,

(3) further cooling the solution under stirring in an ice-water bathdown to 20° C.,

(4) allowing the solution to stand at 20° C. for 3 hours, therebyprecipitating a polymer,

(5) filtering off the precipitated polymer, thereby obtaining afiltrate, and

(6) measuring the amount of the polymer dissolved in the filtrate, whichpolymer is the above soluble parts in xylene at 20° C.

The smaller the CXS value is, the larger stereoregularity the polymerhas.

The above intrinsic viscosity ([η]) was measured at 135° C. using anUbbellohde viscometer in TETRALINE (tetrahydronaphthalene) as a solvent.

The above bulk density was measured according to JIS K 6721 (1966),“JIS” being Japanese Industrial Standard.

Example 2 1. Preparation of a Solid Catalyst Component

Example 1 was repeated except that “washing six times at 105° C. witheach 40 mL of toluene, and further washing three times at a roomtemperature with each 40 mL of hexane” in the step (4) of Example 1 waschanged to “washing five times at 105° C. with each 40 mL of toluene,and further washing three times at a room temperature with each 40 mL ofhexane”, thereby obtaining a solid catalyst component.

The above-obtained solid catalyst component was found to contain 1.7% byweight of titanium atoms, 0.07% by weight of ethoxy groups, 0.16% byweight of butoxy groups, 7.6% by weight of diethyl phthalate, 0.76% byweight of ethyl-n-butyl phthalate, and 2.5% by weight of diisobutylphthalate, the total weight of the solid catalyst component being 100%by weight.

There was added 4.98 g of the above solid catalyst component to 49.8 mLof heptane maintained at 70° C., thereby preparing a suspension of thesolid catalyst component in heptane having a concentration of 0.1g-solid catalyst component/ml-suspension. The prepared suspension wasstirred at 70° C. for 30 minutes, and was filtered with G4 filter. Theobtained filtrate was found to contain titanium atoms in a concentrationof 0.029 mg/ml, measured according to the above method.

2. Polymerization of Propylene

Example 1 was repeated except that 7.81 mg of the solid catalystcomponent was changed to 4.48 mg of the above-obtained solid catalystcomponent, thereby obtaining 203 g of a powdery propylene homopolymer.

A yield of the propylene homopolymer per one g of the solid catalystcomponent was 45,300 g/g. The propylene homopolymer had 0.55% by weightof soluble parts in xylene at 20° C. (CXS), the total weight of thepropylene homopolymer being 100% by weight; an intrinsic viscosity ([η])of 1.68 dl/g; and a bulk density of 0.450 g/mL.

Example 3 1. Preparation of a Solid Catalyst Component

Example 1 was repeated except that “washing six times at 105° C. witheach 40 mL of toluene, and further washing three times at a roomtemperature with each 40 mL of hexane” in the step (4) of Example 1 waschanged to “washing four times at 105° C. with each 40 mL of toluene,and further washing three times at a room temperature with each 40 mL ofhexane”, thereby obtaining a solid catalyst component.

The above-obtained solid catalyst component was found to contain 1.8% byweight of titanium atoms, 0.07% by weight of ethoxy groups, 0.18% byweight of butoxy groups, 7.8% by weight of diethyl phthalate, 0.8% byweight of ethyl-n-butyl phthalate, and 2.5% by weight of diisobutylphthalate, the total weight of the solid catalyst component being 100%by weight.

There was added 4.83 g of the above solid catalyst component to 48 mL ofheptane maintained at 70° C., thereby preparing a suspension of thesolid catalyst component in heptane having a concentration of 0.1g-solid catalyst component/ml-suspension. The prepared suspension wasstirred at 70° C. for 30 minutes, and was filtered with G4 filter. Theobtained filtrate was found to contain titanium atoms in a concentrationof 0.074 mg/ml, measured according to the above method.

2. Polymerization of Propylene

Example 1 was repeated except that 7.81 mg of the solid catalystcomponent was changed to 5.82 mg of the above-obtained solid catalystcomponent, thereby obtaining 292 g of a powdery propylene homopolymer.

A yield of the propylene homopolymer per one g of the solid catalystcomponent was 50,200 g/g. The propylene homopolymer had 0.56% by weightof soluble parts in xylene at 20° C. (CXS), the total weight of thepropylene homopolymer being 100% by weight; an intrinsic viscosity ([η])of 1.60 dl/g; and a bulk density of 0.442 g/mL.

Comparative Example 1 1. Preparation of a Solid Catalyst Component

Example 1 was repeated except that “washing six times at 105° C. witheach 40 mL of toluene, and further washing three times at a roomtemperature with each 40 mL of hexane” in the step (4) of Example 1 waschanged to “washing three times at 105° C. with each 40 mL of toluene,and further washing three times at a room temperature with each 40 mL ofhexane”, thereby obtaining a solid catalyst component.

The above-obtained solid catalyst component was found to contain 2.1% byweight of titanium atoms, 0.06% by weight of ethoxy groups, 0.19% byweight of butoxy groups, 7.7% by weight of diethyl phthalate, 0.8% byweight of ethyl-n-butyl phthalate, and 2.5% by weight of diisobutylphthalate, the total weight of the solid catalyst component being 100%by weight.

There was added 4.55 g of the above solid catalyst component to 46 mL ofheptane maintained at 70° C., thereby preparing a suspension of thesolid catalyst component in heptane having a concentration of 0.1g-solid catalyst component/ml-suspension. The prepared suspension wasstirred at 70° C. for 30 minutes, and was filtered with G4 filter. Theobtained filtrate was found to contain titanium atoms in a concentrationof 0.085 mg/ml, measured according to the above method.

2. Polymerization of Propylene

Example 1 was repeated except that 7.81 mg of the solid catalystcomponent was changed to 8.21 mg of the above-obtained solid catalystcomponent, thereby obtaining 432 g of a powdery propylene homopolymer.

A yield of the propylene homopolymer per one g of the solid catalystcomponent was 52,600 g/g. The propylene homopolymer had 0.62% by weightof soluble parts in xylene at (CXS), the total weight of the propylenehomopolymer being 100% by weight; an intrinsic viscosity ([η]) of 1.66dl/g; and a bulk density of 0.443 g/mL.

1. A solid catalyst component for olefin polymerization, comprisingtitanium atoms, magnesium atoms, halogen atoms and hydrocarbyloxygroups, wherein the following filtrate contains titanium atoms in aconcentration of 0.08 mg-Ti/ml-filtrate or lower, measured according toa method comprising the steps of: (1) preparing a suspension of thesolid catalyst component for olefin polymerization in heptane having aconcentration of 0.1 g-solid catalyst component/ml-suspension; (2)heating the suspension at 70° for 30 minutes under stirring; (3)filtering the suspension, thereby obtaining a filtrate; and (4)measuring a concentration of titanium atoms contained in the filtrate.2. The solid catalyst component for olefin polymerization according toclaim 1, wherein the filtrate contains titanium atoms in a concentrationof 0.05 mg-Ti/ml-filtrate or lower.
 3. The solid catalyst component forolefin polymerization according to claim 1, wherein the filtratecontains titanium atoms in a concentration of 0.04 mg-Ti/ml-filtrate orlower.
 4. The solid catalyst component for olefin polymerizationaccording to claim 1, wherein the filtrate contains titanium atoms in aconcentration of 0.03 mg-Ti/ml-filtrate or lower.
 5. The solid catalystcomponent for olefin polymerization according to claim 1, wherein thesolid catalyst component comprises 0.1 to 3.0% by weight of titaniumatoms, 5 to 30% by weight of magnesium atoms, 40 to 70% by weight ofhalogen atoms and 0.1 to 3.5% by weight of hydrocarbyloxy groups, thetotal weight of the solid catalyst component being 100% by weight. 6.The solid catalyst component for olefin polymerization according toclaim 1, wherein the halogen atom is a chlorine atom.
 7. The solidcatalyst component for olefin polymerization according to claim 1,wherein the hydrocarbyloxy group is an ethoxy group and/or butoxy group.8.-14. (canceled)